Process for producing ethylenically unsaturated aliphatic nitriles

ABSTRACT

PROCESS FOR PRODUCING ETHYLENICALLY UNSATURATED ALIPHATIC NITRILES OF ACRYLONITRILE, METHACRYLONITRILE, CROTONITRILE, 1-CYANO-BUTENE-1, 2-CYANO-BUTENE-1, 2-CYANO-BUTENE-2 AND 1-CYANO-2-METHYL-PROPENE-1, BY REACTING AN OLEFINIC HYDROCARBON CONTAINING 2 TO 4 CARBON ATOMS I.E. ETHYLENE, PROPYLENE, NORMAL BUTYLENE AND ISOBUTYLENE WITH HYDROGEN CYANIDE AND OXYGEN OR A MOLECULAR OXYGEN CONTAINING GAS IN THE GASEOUS PHASE IN THE PRESENCE OF A CATALYST SELECTED FROM THE GROUP CONSISTING OF THE OXIDES OF RHODIUM SELECTED FROM THE GROUP CONSISTING OF RHO, RH2O3, RHO3 AND RHO2; THE HYDROXIDES OF PALLADIUM AND RHODIUM SELECTED FROM THE GROUP CONSISTING OF PD(OH)2, PD(OH)4, RH(OH)3 AND RH(OH)4; THE CHLORIDES OF PALLADIUM AND RHODIUM SELECTED FROM THE GROUP CONSISTING OF PDCL, PDCL2, PDCL3, PDCL4, RHCL2 AND RHCL3; THE BROMIDES OF PALLADIUM AND RHODIUM SELECTED FROM THE GROUP CONSISTING OF PDBR2 AND RHBR3; THE NITRATES OF PALLADIUM AND RHODIUM SELECTED FROM THE GROUP CONSISTING OF PD(NO3)2 AND RH(NO3)3; PD(CH)2 AND PD(OCOCH3)2 AT A TEMPERATURE OF 200*C.

United States Patent O 3,574,701 PROCESS FOR PRODUCING ETHYLENICALLYUNSATURATED ALIPHATIC NITRILES Naoya Kominami, Tokyo, Hitoshi Nakajima,Urawa-shi, and Nobuhiro Tamura, Tokyo, Japan, assignors to Asachi KaseiKogyo Kabushiki Kaisha, Asaka, Japan No Drawing. Continuation-impart ofapplication Ser. No. 489,750, Sept. 23, 1965. This application May 6,1969, Ser. No. 822,300 Claims priority, application Japan, Oct. 15,1964, 39/5s,s44 Int. Cl. C07c 121/04 US. Cl. 260-465.3 Claims ABSTRACTOF THE DISCLOSURE Process for producing ethylenically unsaturatedaliphatic nitriles of acrylonitrile, methacrylonitrile, crotonitrile,l-cyano-butene-l, 2-cyano-buteue-1, 2-cyano-butene-2 and1-cyano-2-methyl-propenel, by reacting an olefinic hydrocarboncontaining 2 to 4 carbon atoms i.e. ethylene, propylene, normal butyleneand isobutylene with hydrogen cyanide and oxygen or a molecular oxygencontaining gas in the gaseous phase in the presence of a catalystselected from the group consisting of the oxides of rhodium selectedfrom the group consisting of RhO, Rh O RhO and RhO the hydroxides ofpalladium and rhodium selected from the group consisting of Pd(OH)Pd(OH) Rh(OH) and Rh(OH) the chlorides of palladium and rhodium selectedfrom the group consisting of PdCl, PdCl PdCl PdCl RhCl and RhCl thebromides of palladium and rhodium selected from the group consisting ofPdBr and RhBr the nitrates of palladium and rhodium selected from thegroup consisting of Pd(NO and Rh(NO Pd(CN) and Pd(OCOCH at a temperatureof 200 C.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of U.S. application Ser. No. 489,750 :tiled Sept.23, 1965, now abandoned.

BACKGROUND OF THE INVENTION (1) Field of the invention This inventionrelates to a process for producing ethylenically unsaturated aliphaticnitriles by subjecting a gaseous mixture of an olefinic hydrocarboncontaining 2 to 4 carbons, hydrogen cyanide and oxygen or a molecularoxygen containing gas to a gaseous phase catalyst reaction in thepresence of a catalyst.

(2) Description of the prior art Hitherto, there has been no commercialprocess according to which ethylenically unsaturated aliphatic nitrilescan be prepared directly in a single step directly from an olefinichydrocarbon containing 2 to 4 carbon atoms, hydrogen cyanide and oxygenby a gaseous phase catalytic reaction.

It is an object of the present invention to provide a process accordingto which ethylenically unsaturated aliphatic nitriles can be prepareddirectly in a single step by a gaseous phase catalytic reaction of anolefinic hydrocarbon containing 2 to 4 carbon atoms, hydrogen cyanideand oxygen or a molecular oxygen containing gas.

Other objects and advantages will become apparent from the followingdescription.

SUMMARY OF THE INVENTION According to the present invention anethylenically unsaturated aliphatic nitrile is prepared by reacting anole- 3,574,701 Patented Apr. 13, 1971 "Ice finic hydrocarbon containing2 to 4 carbon atoms selected from the group consisting of ethylene,propylene, normal butylene and isobutylene with hydrogen cyanide and agas consisting of oxygen and molecular oxygen containing gases in thegaseous phase in the presence of a catalyst selected from the groupconsisting of the oxides of rhodium selected from the group consistingof RhO, -Rh O RhO and RhO the hydroxides of palladium and rhodiumselected from the group consisting of Pd(OH) Pd(OH) Rh(OH) and Rh(OH)the chlorides of palladium and rhodium selected from the groupconsisting of PdCl, PdCl PdCl PdCl RhCl and RhCl the bromides ofpalladium and rhodium selected from the group consisting of PdBr and'RhBr the nitrates of palladium and rhodium selected from the groupconsisting of Pd(NO and Rh(NO Pd(CN) and Pd(OCOCH at a temperature of200 C. to 500 C.

The present process may be represented by the following equation:

O=CHR3 1120 wherein R R and R are independently selected from the groupconsisting of hydrogen, methyl and ethyl.

The olefinic hydrocarbons containing 2 to 4 carbon atoms which may beused as feedstocks according to the present invention include ethylene,propylene, normal butylene and isobutylene The main products of theethylenically unsaturated aliphatic nitriles are acrylonitrile fromethylene; methacrylonitrile and crotononitrile from propylene;l-cyanobutene-l, Z-cyano-butene-l and 2-cyano-butene-2 from normalbutylene; and 1-cyano-2-methyl-propene-l from isobutylene. Moreover, itis possible to by-produce proionitrile from ethylene; butyronitrilesfrom propylene; valeronitrile from butylenes and acetonitrile in eachcase.

The volume ratio of the olefinic hydrocarbon to hydrogen cyanide in thestarting gaseous mixture is preferably in the range of 1:20 to 20:1 andthe volume ratio of oxygen to combined hydrogen cyanide and the olefinichydrocarbon is preferably at most one.

In practising the process of the present invention, the presence of aninert gas or a relatively low reactive gas is not necessarily requiredbut is not objectionable. Examples of inert gas or gas of low reactivitywhich may be present in a starting gas mixture include nitrogen, carbondioxide, carbon monoxide, steam, methane, ethane, propane and butane.

The catalysts according to the present invention include the oxides ofrhodium selected from the group consisting of RhO, Rh O RhO and 'RhO thehydroxides of palladium and rhodium selected from the group consistingof Pd(OH) Pd(OH) Rh(OH) and Rh(OH) the chlorides of palladium andrhodium selected from the group consisting of PdCl, PdCl PdCl PdCl RhCland RhOl the bromides of palladium and rhodium selected from the groupconsisting of PdBr and RhBr the nitrates of palladium and rhodiumselected from the group consisting of Pd(NO and -Rh(NO Pd(CN) andPd(OCOCH The use of a carrier is not essential but is preferable. Thecarrier may be any one that can be usually employed as carrier. Exampleof suitable carriers are silica, silicaalumina, alumina, active carbon,coke and diatomaceous earth.

The catalyst for use in the process of this invention may be prepared bysupporting the component of the catalyst on a carrier by any of theconventional methods such as the immersing method, the mixing method orthe heating method.

The temperature adopted for carrying out the process of the presentinvention is in the range of 200 C. to 500 C.

The pressure at which process is effected may be atmospheric. Thereaction may also be etfected under pressure.

The space velocity to be used in the present invention is preferably inthe range of 20 hr." to 5,000 hI.

This invention will now be illustrated by the following examples inwhich percents are all by mol unless expressly stated to contrary.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1 8.4 g. of PdCl wasdissolved in 200 ml. of a 1 N hydrochloric acid and 100 ml. of granularactive carbon was immersed therein and the whole mixture was evaporatedto dryness on a hot Water bath. The resulting mixture was heated at 300C. for 3 hours in a steam of hydrogen gas to reduce the PdCl to metallicpalladium. 10 ml. of this catalyst was filled into a U-shaped reactiontube of heat-resistance glass of 17 mm. inside diameter. The reactiontube was maintained at 315 C. and a gas mixture consisting of ethylene,hydrogen cyanide, oxygen, nitrogen and carbon dioxide at a volume ratioof 3:4:1:10:2 was introduced at a space velocity of 480 hr.- As a resultof reaction for 80 minutes, the yield of acryonitrile based on theintroduced ethylene was 20.1% and the yiel dof propionitrile based onthe introduced hydrogen cyanide was 13.0%.

Example 2 4.2 g. of PdCl was dissolved in 200 ml. of a 1 N hydrochloricacid and 100 ml. of granular active carbon was immersed therein and themixture was evaporated to dryness on a hot Water bath. ml. of thiscatalyst was mixed with 5 ml. of quartz sand and filled into the samereaction tube as in Example 1. The reaction tube was maintained at 250C. and a gas mixture consisting of ethylene, hydrogen cyanide, oxygenand nitrogen at a volume ratio of 612:1:8 was introduced at a spacevelocity of 510 hr. As a result of reaction for one hour, the yields ofacrylonitrile and propionitrile based on the introduced hydrogen cyanidewere 16 and 1.8% respectively.

Example 3 sisting of ethylene, hydrogen cyanide and air at a volumeratioof 4:223 was introduced at a flow rate of 60 ml./ min. As a result ofreaction for one hour, the yields of acrylonitrile and propionitrilebased on the introduced hydrogen cyanide were 1.7% and 0.3%respectively.

Example 4 5 g. of Pd(ON) was dissolved in 500 ml. of an aqueous ammoniasolution and 160 ml. of active carbon was immersed therein and themixture was evaporated to dryness on a hot water bath. ml. of thiscatalyst was filled into the same reaction tube as in Example 1. Thereaction tube was maintained at 300 C. and a gas mixture consisting ofpropylene, hydrogen cyanide, air and propane at a volume ratio of2:1:l:2 'Was introduced at a space velocity of 120 1112 As a result ofreaction for one hour, the yields of acetonitrile, acrylonitrile,methacrylonitrile, isobutyronitrile, normal butyronitrile andcrotononitrile based on the introduced hydrogen cyanide were 1.1%, 0.4%,7.1%, 2.4%, 4.8% and 6.4%, respectively.

Example 5 10 ml. of the same catalyst as in Example 4 was filled 4 intothe same reaction tube as in Example 1. The reaction tube was maintainedat 300 C. and a gas mixture consisting of normal butylene, hydrogencyanide, air and nitrogen at a volume ratio of 3:l:1:2 was introduced ata space velocity of 120 hr. The normal butylene in the gas mixture had apurity of and the mixture also contained normal butane and isobutane. Asa result of reaction for one hour, the yields of acetonitrile,acrylonitrile, cyanobutenes and cyanobutane based on the introducedhydrogen cyanide were 4.1%, 2.3%, 6.8% and 8.1%, respectively.

Example 6 5 ml. of the same catalyst as in Example 2 was mixed with 5ml. of quartz sand and filled into the same reaction tube as inExample 1. The reaction tube was maintained at 320 C. and a gas mixtureconsisting of isobutylene, hydrogen cyanide, air and nitrogenat a volumeratio of 2:1:1:1 was introduced at a space velocity of 550 hr.- As aresult of reaction for one hour, the yield of 1-cyano-2methyl-propene-1based on the introduced hydrogen cyanide was 10.3%.

Example 7 6.1 g. of PdBr was added to 500 ml. of an aqueous 10% hydrogenbromide solution, and ml. of active carbon were immersed therein and themixture was evaporated to dryness on a hot water bath. 5 ml. of thiscatalyst was mixed with 5rnl. of quartz sand and filled into the samereaction tube as in Example 1. The reaction tube was maintained at 250C. and a gas mixture consisting of ethylene, hydrogen cyanide, air,nitrogen and steam at a volume ratio of 10:5: 15:29-z1 was introduced ata space velocity of 280 hrs- As a result of reaction for one hour, theyields of acrylonitrile and propionitrile based on the introducedhydrogen cyanide were 3.1% and 2.3% respectively.

Example 8 1 00 m1. of pulverized coke was immersed in 200ml. of anaqueous solution containing 4.0 g. of 'RhCl and the mixture wasevaporated to dryness on a hot water bath. 10 ml. of this catalyst wasfilled into the same reaction tube as in Example 1. The reaction tubewas maintained at 300 C. and a gas mixture consisting of ethylene,hydrogen cyanide, air and nitrogen at a volume ratio of 2:1:2:5 wasintroduced at a space velocity of 240 hrr As a result of a reaction forone hour, the yields of acrylonitrile and propionitrile based on theintroduced hydrogen cyanide were 2.1% and 0.4% respectively.

Example 9 5 ml. of the same catalyst as in Example 8 was mixed with 5ml. of quartz sand and filled into the same reaction tube as inExample 1. The reaction tube was maintained at 350 C. and a gas mixtureconsisting of butylenes, hydrogen cyanide, air and nitrogen at a volumeratio of 3:1:1:2 Was introduced at a space velocity of 200 1312- Thebutylenes in the gas mixture consisted of 50% by volume of normalbutylene and 50% by volume of iso butylene. As a result of reaction forone hour, the yields of cyanobutenes and 1-cyano-2-methyl-propene-1based on the introduced hydrogen cyanide were 3.5% and 3.1%respectively.

Example 10 ml. of granular active alumina was immersed in I 200 ml. ofan aqueous solution containing 5 g. of Pd(N0 and the mixture wasfiltered 0ft. 5 ml. of this catalyst was mixed with 5 ml. of quartz sandand filled into the same reaction tube as in Example 1. The reactiontube was maintained at 300 C. and a gas mixture consisting of ethylene,hydrogen cyanide, air and nitrogen at a volume ratio of 3:1:3z2 wasintroduced at a space velocity of 1020 hrr As a result of reaction forone hour, the yields of acrylonitrile and propionitrile based on theintroduced hydrogen cyanide was 3.6% and 2.1% TABLE 1 respectively.Yield of acryloni- Example 11 Temperature C.): trile (mol percent) ml.of the same catalyst as in Example 10 was heated in air at 350 C. for 3hours to decompose the Pd(NO 5 250 to PdO. 10 ml. of this catalyst wasfilled into the same 300 reaction tube as in Example 1 and the reactiontube was 350 n 4 maintained at 320 C. A gas mixture consisting of eth-400 ylene, hydrogen cyanide, air and nitrogen at a volume 470 ratio of121:2:6 was introduced at a space velocity of 10 500 640 hr.- As aresult of reaction for one hour, the yields n of acetonitrile,acrylonitrile and propionitrile based on ExamP the introduced hydrogencyanide were 1.7%, 3.8% and 42 g. of Pdclg was dissolved in 100 m1. of a1 N 43% respectively' 15 hydrochloric acid, and 50 ml. of granularactive carbon Example 12 was immersed therein and the mixture wasevaporated to 100 ml. of silica gel powder was immersed in 200 ml.dryness p a hot Water brfuh reheated 5 of this of an aqueous acetic acidsolution containing 2.1 g. of catalyst Pdcl was mlxed Wlth 5 of quartzSand Pd(OCOCH and the mixture was filtered off and the and fined.int theSame F i tube as Example precipitates were dried at 50 C. in vacuoovernight. The Ieactlon tube was mamtamed at 250 and a gas 15 m1. ofthis catalyst was filled into the same reaction F Consisting ofethylenfi" hydrogen cyanifie oxygen tube as in Example 1 and thereaction tube was main and nltrogen at a volume ratio of 632:1:8 wasintroduced tained at 250 C. A gas mixture consisting of ethylene, at aSpace velocltypf 510 A result of hydrogen cyanide, air and nitrogen at avolume ratio of for one hour, the yields of acrylomtnle andpr0p1on1tr1le 3:1:2z4 was introduced at a space velocity of 370 hrrbased on the mtrfxmced hydrogen cyamde were 159% As a result of reactionfor 2 hours, the yields of acryloand 16% respectlvelynitrile andpropionitrile based on the introduced hydro- E l 16.

gm cyamde were 51% and 15% respectlvely' 2.5 g. of metallic palladiumwas dissolved in 100 ml.

E l 13 of aqua regia and 50 ml. of granular active carbon and themixture was evaporated to dryness. 5 ml. of this catalyst, i.e. PdCl wasmixed with 5 ml. of quartz sand and filled into the same reaction tubeas in Example 1. The reaction tube was maintained at 250 C. and a gasmixture consisting of ethylene, hydrogen cyanide, oxygen and nitrogen ata volume ratio of 6:2: 1:8 was introduced 'at a space velocity of 510hr.- As a result of reaction for one hour, the yields of acrylonitrileand propionitrile based on the introduced hydrogen cyanide were 16.1% 40and 1.7% respectively.

2.1 g. of PdCl was supported on 100 ml. of diatomaceous earth in thesame manner as in Example 1. 10 ml. of this catalyst was filled into thesame reaction tube as in Example 1 and the reaction tube was maintainedat 350 C. A gas mixture consisting of ethylene, hydrogen 35 cyanide, airand nitrogen at a volume ratio of 221:2:2 was introduced at a spacevelocity of 240 hr.- As a result of reaction for one hour, the yields ofacetonitrile, acrylonitrile and propionitrile based on the introducedhydrogen cyanide were 0.9%, 8.1% and 0.1% respectively Examples 17 to 28Example 14 5 ml. of the catalyst was mixed with 5 ml. of quartz sand andfilled into a reaction tube of heat-resistance of Pdclz was dlssolved200 of a 1 N glass having 17 mm. inside diameter. A gas mixturehavhydrochloric acid, and 100 ml. of alumina was immersed ing a ifi dcomposition at a ifi d volume m, th The Whole IIllXtufe Was P to drynesswas fed into the reaction tube maintained at a temperaon a hot waterbath. 5 ml. of the resulting catalyst was r between 280 C. and 450 C. ata space velocity mixed with 5 m1. of quartz sand and charged into areacbetween 220 hr.- and 640 hrf The reaction conditions tion tube ofquartz glass having 17 mm. inside diameter. and results are shown inTable 2.

TABLE 2 Reactants (volume ratio) Yield of products* (3.1100 ReactionSpace ml. temperavelocity Acrylo- Propio- Example No. Catalyst carrierCarrier ture C.) (hrr CzHi HCN 02 N2 Air nitrlle nltrlle 17 Pd(OH)z 1.4$10; 350 300 4 3 3 6.2 1.5 1. si 350 300 4 3 a 5.9 1.6 2. 250 510 s 2 s16.2 1. 5 1. 450 520 3 1 2 2 4.5 0.8 2, 450 520 3 1 2 2 4.2 0.82 1. 450520 3 1 2 2 4.3 0. 19 1. 450 520 3 1 2 2 4. 2 0. 77 1. 350 220 5 1 5 3.91.2 1. 350 220 5 1 5 4.0 1.1 2. 280 270 3 2 2 3.4 0.8 1. 300 240 2 1 5 22. 2 0. 35 3. 360 320 1 1 1 3.1 0.5

*Yields of products in 11101 percent based on the introduced hydrogencyanide as a result of reaction for one hour.

A gas mixture consisting of ethylene, hydrogen cyanide, What is claimedis:

oxygen and nitrogen at a volume ratio of 222:1:8 was 7 1. A process forthe production of at least one ethylfed to the reaction tube maintainedat a temperature enically unsaturated aliphatic nitrile selected fromthe between 200 C. and 500 C. at a space velocity of 500 groupconsisting of acrylonitrile, methacrylonitrile, crohr.- As a result ofreaction for one hour the yields of tononitrile, l-cyanobutene-l,2-cyano-butene-1, 2-cyanoacrylonitrile in mol percent based on theintroduced butene-2 and 1-cyano-2-methylpropene-1, said process hydrogencyanide were shown in Table 1. comprising reacting at least one olefinichydrocarbon containing 2 to 4 carbon atoms selected from the groupconsisting of ethylene, propylene, normal butylene and isobutylene withhydrogen cyanide and a gas selected from the group consisting of oxygenand molecular oxygen containing gases in the gaseous phase in thepresence of a catalyst selected from the group consisting of the oxidesof rhodium selected from the group consisting of RhO, Rh O R110 and RhOthe hydroxides of palladium and rhodium selected from the groupconsisting of Pd(OH) Pd(OH) Rh(OH) and Rh(OH) the chlorides of palladiumand rhodium selected from the group consisting of PdCl, PdCI PdCl PdClRhCl and RhCl the bromides of palladium and rhodium selected from thegroup consisting of PdBr and RhBr the nitrates of palladium the groupconsisting of PdBr and RhBr the nitrates of palladium and rhodiumselected from the group consisting of Pd(NO and Rh(NO Pd(CN) andPd(OCOCH at a temperature of 200 C. to 500 C.

2. A process according to claim 1 wherein the catalyst 0 is supported ona carrier selected from the group consisting of silica, silica-alumina,alumina, active carbon, coke and diatomaceous earth.

3. A process according to claim 1 wherein the reaction is effected inthe presence of at least one gas selected from the group consisting ofnitrogen, carbon monoxide, carbon dioxide, steam, methane, ethane,propane and butane.

4. A process according to claim 1 wherein the olefinic hydrocarboncontaining 2 to 4 carbon atoms and the hydrogen cyanide are present in avolume ratio of 1:20 to 20:1 and the oxygen is present in an amount ofat most one volume per volume of combined hydrogen cyanide and olefinichydrocarbon containing 2 to 4 carbon atoms.

5. A process according to claim 1 wherein a gaseous mixture of theolefinic hydrocarbon containing 2 to 4 carbon atoms, hydrogen cyanideand the oxygen containing gas is passed on the catalyst at a spacevelocity between 20 hr." and 5,000 hl'.'"

References Cited UNITED STATES PATENTS 3,347,900 10/1967 Gossel et al.260465.3 v 3,470,230 9/1969 Hirsch et al. 260465.3

JOSEPH PAUL BRUST, Primary Examiner UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent 3.574 .701 Dated March 16 1971 NaoyaKominami et a1 It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

In the heading to the printed specification, lines 5 and I "assignors toAsachi Kasei Kogyo Kabushiki Kaisha, Asaka, Japan should read assignorsto Asahi Kasei Kogyo Kabushiki Kaisha Asaka, Japan Signed and sealedthis 22nd day of February 1972 (SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patent:

